Di- and triepoxtoe derivatives of
trivinylcyclohexane



United States Patent 2 Claims. Cl. 260348) This application is adivision of our appl cation Serial No. 41,047, filed July 6, 1960, andnow abandoned.

The present invention is concerned with diepoxide and tn'epoxidederivatives of 1,2,4-trivinylcyclohexane. The new compounds are usefulfor the production of epoxide resins, polyester and polymers. Moreoverthe new compounds are especially active as stabilizers forpolyvinylchloride.

In the epoxidation of 'l,2,4-trivinylcyclohexane it is possible,depending upon the reaction conditions selected to produce not onlymonoepoxides but also the diand triepoxides.

Trivinylcyclohexane which readily 'may be made for example by thermal orcatalytic isomerization of 1,5,9- cyclododecatriene may be used as thestarting material. Organic peracids such as performic acid, peraceticacid or perbenzoic acid or the corresponding aldehydemonoperacylate maybe used as the oxidizing agent. The peracid may also be formed fromhydrogen peroxide during the course of the reaction. The epoxidationreaction may be carried out in the presence or absence of solvents suchas benzene, acetone or chloroform. The appropriate reaction temperaturedepends upon the particular epoxide being formed and the particularprocedure employed but generally is within the range from 20 to 80 C.The process generally is carried out by adding the peracid dropwise withstirring to the compound to be epoxidized. When using anacetaldehydemonoperacetate solution the reaction is carried out invacuum so that the solvent and the acetaldehyde coming from theperacylate during reaction are distilled. The progress of the reactionis determined by titration of the peroxide content. After the end of thereaction the epoxide is recovered either by direct distillation of thereaction mixture or after washing out the acid. In the case of the monoand diepoxides mixtures of different isomers are obtained.

The invention is further described and illustrated by the followingspecific examples.

Example 1 2000 parts by weight of a 17.6% solution of peracetic acid inacetone are introduced with stirring into 800 parts Patented May 17,1966 cyclohexanediepoxide having a boiling point of 8495 C. at 0.3 torr(n =l.4906).

Example 2 40 parts by weight of a diepoxyethylvinylcyclohexane mixturewas heated for 34 hours at 30 C. with parts by weight of a 22.6%solution of peracetic acid in acetone. The resulting reactionmixturecontains still about 5 parts by weight of peracetic acid. The reactionmixture is taken up in benzene and the resulting solution is washed withan aqueous soda solution and then dried and distilled. 6 parts by weightof unreacted diepoxyethylvinylcyclohexane distill at IDS-115 C. at apressure of 0.2 torr and 12 parts by weight of1,2,4-triep0xyethylcyclohexane =(n "=1.4937) distill at 125- l35 C. atthe same pressure. The conversion is and the yield is 33% of thetheoretical yield.

Example 3 (n =1.4854) distilled at 58-65 C. under a pressure. of 0.3torr.

Example 4 A mixture of 500 parts by weight of trivinylcyclohexane, 175parts 'by weight of a 30% solution of hydrogen peroxide and 35 parts byweight of formic acid was stirred for 3 days at room temperature. 70% ofthe hydrogen peroxide were consumed. The aqueous phase was separated andreplaced by 175 parts by weight of fresh hydrogen peroxide and 35 partsby weight of formic acid. After 3 more days the operation was repeated.After a total of '9 days the aqueous layer was separated and the organicphase was washed with a dilute water solution of sodium hydroxide, thendried over anhydrous sodium sulfate and there rectified. 234 parts byweight of unchanged trivinylcyclohexane, corresponding to a conversionof 53% and '152 parts by weight of monoepoxyethyldivinylcyclohexane (BP.57-64 C. at 0.5 torr, n 1.48'491.4858) corresponding to a yield of 51%were recovered.

Example 5 were added dropwise with stirring to a solution of 15 parts byweight of perbenzoic acid in 400 parts by weight of chloroform. .After24 hours of the perbenzoic acid was consumed. The resulting solution waswashed with a dilute solution of sodium hydroxide in water and thendried over sodium sulfate and distilled. 11 parts by weight of1,2,4-triepoxyethylcyclohexane (n =1.4942) distilled over at -30 C. at apressure of 0.5 torr. The yield was 53% of the theoretical yield.

We claim:

1. Isomer mixture of diepoxides of 1,2,4-trivinylcyclohexane having aboiling point of 8495 at 0.3 torr and a refractive index n- ='1.4906.

2. 1,2,4-triepoxyethylcyclohexane.

(References on following page) 3 I 4 References Cited by the ExaminerOTHER REFERENCES UN T S TES PATENTS Hendry et 2 .1., Brit. J. Pharmacol,1951,1vo1. 6, pages 2,887,465 5/1959 Hopif 260348 235-255 '(pages 238and 242 relied on). 2,977,374 3/ '1961 Phillips et a1 2'60348 5 FOREIGNPATENTS WALTER A. MODANCE, Primary Examiner. 488,698 12/ 1952 Canada.DUVAL T. MCCUTCHEN, Examiner.

1,011,410 4/1952 France.

1. ISOMER MIXTURE OF DIEPOXIDES OF 1,2,4-TRIVINYLCYCLOHEXANE HAVING ABOILING POINT OF 84-95 AT 0.3 TORR AND A REFRACTIVE INDEX NP20=1.4906.2. 1,2,4-TRIEPOXYETHYLCYCLOHEXANE.